CN115558098A - Preparation method of polymer with micropores - Google Patents
Preparation method of polymer with micropores Download PDFInfo
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- CN115558098A CN115558098A CN202211209361.8A CN202211209361A CN115558098A CN 115558098 A CN115558098 A CN 115558098A CN 202211209361 A CN202211209361 A CN 202211209361A CN 115558098 A CN115558098 A CN 115558098A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 48
- 239000002994 raw material Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 13
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 12
- 125000003277 amino group Chemical group 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 120
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 74
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 239000008367 deionised water Substances 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- 239000012298 atmosphere Substances 0.000 claims description 26
- 239000012043 crude product Substances 0.000 claims description 23
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 238000000967 suction filtration Methods 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000012153 distilled water Substances 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 6
- 239000003607 modifier Substances 0.000 claims description 6
- 239000003880 polar aprotic solvent Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 125000001302 tertiary amino group Chemical group 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims description 2
- 238000013375 chromatographic separation Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 13
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002253 acid Substances 0.000 abstract description 9
- 238000009792 diffusion process Methods 0.000 abstract description 8
- 239000012528 membrane Substances 0.000 abstract description 8
- 238000000502 dialysis Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 230000004907 flux Effects 0.000 abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000010534 nucleophilic substitution reaction Methods 0.000 abstract description 3
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 238000000909 electrodialysis Methods 0.000 abstract description 2
- 239000012982 microporous membrane Substances 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 26
- 238000004440 column chromatography Methods 0.000 description 13
- PBPCCBLJHAAYFD-UHFFFAOYSA-N tetraphen-1-ol Chemical compound C1=CC=CC2=CC3=C4C(O)=CC=CC4=CC=C3C=C21 PBPCCBLJHAAYFD-UHFFFAOYSA-N 0.000 description 12
- 239000012046 mixed solvent Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000010907 mechanical stirring Methods 0.000 description 10
- PCRSJGWFEMHHEW-UHFFFAOYSA-N 2,3,5,6-tetrafluorobenzene-1,4-dicarbonitrile Chemical compound FC1=C(F)C(C#N)=C(F)C(F)=C1C#N PCRSJGWFEMHHEW-UHFFFAOYSA-N 0.000 description 8
- 239000003011 anion exchange membrane Substances 0.000 description 6
- WRXNJTBODVGDRY-UHFFFAOYSA-N 2-pyrrolidin-1-ylethanamine Chemical compound NCCN1CCCC1 WRXNJTBODVGDRY-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- JXISJBVJNUKKBK-UHFFFAOYSA-N 2,3,5,6-tetrafluoropyridine-4-carbonitrile Chemical compound FC1=NC(F)=C(F)C(C#N)=C1F JXISJBVJNUKKBK-UHFFFAOYSA-N 0.000 description 3
- -1 hydrogen ions Chemical class 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- RWIVICVCHVMHMU-UHFFFAOYSA-N n-aminoethylmorpholine Chemical compound NCCN1CCOCC1 RWIVICVCHVMHMU-UHFFFAOYSA-N 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- CJNRGSHEMCMUOE-UHFFFAOYSA-N 2-piperidin-1-ylethanamine Chemical compound NCCN1CCCCC1 CJNRGSHEMCMUOE-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- MRRWKFVZIOCJBS-UHFFFAOYSA-N benzo[a]anthracen-3-ol Chemical compound C1=CC=C2C=C3C4=CC=C(O)C=C4C=CC3=CC2=C1 MRRWKFVZIOCJBS-UHFFFAOYSA-N 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
- C08G65/4031—(I) or (II) containing nitrogen
- C08G65/4037—(I) or (II) containing nitrogen in ring structure, e.g. pyridine group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
- C08G65/4031—(I) or (II) containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
- C08G65/4056—(I) or (II) containing sulfur
- C08G65/4062—(I) or (II) containing sulfur in ring structure
Abstract
The invention discloses a preparation method of a polymer with micropores, which takes synthesized tetraphenol monomer containing Cardo group and strong rigid cyclic amine group structure as raw materials, and prepares the soluble polymer with micropores by nucleophilic substitution copolymerization with tetrahalogen monomer A. The synthesized self-contained microporous polymer has the characteristics of strong adjustability of chemical structure, easily obtained raw materials, low price, simple synthesis steps and the like. The method not only can inherit and develop the advantage of high selectivity of the cyclic ammonium phenolphthalein polyarylethersulfone membrane in the process of recovering diffusion dialysis acid, but also is expected to have the advantages of excellent stability and high flux of the self-polymerization microporous membrane material, and has wide application prospect in the fields of gas separation, diffusion dialysis, electrodialysis and the like.
Description
Technical Field
The invention belongs to the technical field of polymer preparation, and particularly relates to a preparation method of a self-polymerization microporous polymer.
Background
The harmless and recycling treatment of the acidic waste liquid is one of the hot problems in the environmental field. Currently, among the various treatment methods, the Diffusion Dialysis (DD) technique, which is based on an Anion Exchange Membrane (AEM) as core, is a membrane separation technique using a concentration gradient as driving force, which mainly uses hydrogen ions (H) + ) With metal ions (M) of different kinds and valences n+ ) The difference in diffusion in selective AEM allows for separate recovery of the acid. The technology has the advantages of energy conservation, environmental protection, capability of recycling the waste acid and the like, and is a waste acid resource utilization technology with a very promising prospect. However, AEM for DD acid recovery generally faces poor selectivity bottleneck at present, so that DD process is greatly limited in the field of waste acid separation and recovery. Recently, gong (J.Membr.Sci.624 (2021), 119115.) et al prepared a series of phenolphthalein polyarylethersulfones containing different cyclic amine groups by nucleophilic substitution copolymerization using cyclic amine phenolphthalein diphenol monomers, dihalogenated hydrocarbon monomers, and corresponding comonomers,then a series of anion exchange membranes are prepared through quaternization, due to the unique Cardo group and strong rigid cyclic ammonium group structure of the material, the series of membranes show ultrahigh selectivity in the process of diffusion dialysis acid recovery, but the acid flux of the series of membranes is required to be further improved. The polymer microporous material serving as a separation membrane material is often characterized by high flux and high selectivity, and is considered as an effective means for solving the problem that the high flux and the selectivity of the traditional separation membrane cannot be achieved at the same time.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a polymer with micropores.
In order to realize the task, the invention adopts the following technical scheme:
the preparation method of the polymer with micropores is characterized in that the method comprises the steps of mixing a tetraphenol monomer, a tetrahalogen monomer A and NaOH or K 2 CO 3 Or Cs 2 CO 3 Or Na 2 CO 3 According to the mass ratio of 1:1: 2-9, then adding the mixture and a proper amount of anhydrous polar aprotic solvent and toluene or cyclohexane into a reactor provided with a water separator, heating the mixture in a constant-temperature oil bath at 120-130 ℃, azeotropically taking out water generated by the reaction by the toluene or cyclohexane, reacting for 2-3 h, evaporating the azeotropic toluene or cyclohexane, continuing heating the mixture in a constant-temperature oil bath at 100-180 ℃, reacting for 3-10 h, slowly pouring the viscous solution into deionized water, performing suction filtration to obtain a fibrous polymer, washing the fibrous polymer for 3-5 times by distilled water, and drying the fibrous polymer to constant weight at 100-130 ℃ under a vacuum condition to obtain the self-microporous polymer containing side chain amino groups; wherein:
the synthetic method of the tetraphenol monomer is that N is 2 In the atmosphere, raw materials and raw material modifiers are mixed according to the mass ratio of 1: 2-7, reacting in a constant temperature oil bath at 100-200 ℃ for 1-10 d by using a polar aprotic solvent, slowly pouring the reacted viscous solution into deionized water, performing suction filtration and drying to obtain a crude product, and performing recrystallization or column chromatography separation to obtain a corresponding tetraphenol monomer;
the structural formula of the raw material is as follows:
the structural general formula of the raw material modifier is as follows:
NH 2 -R；
wherein R has the structural formula:
in the formula, R 1 、R 2 And R 3 The group is an aliphatic chain structure consisting of 0-12C and O elements in length, wherein R 2 The connecting position of the group on the cyclic amine ring is any position;
the structure of the prepared polymer with micropores is shown as the following formula:
according to the present invention, the structural formula of the prepared tetraphenol monomer is as follows:
in the formula, R is fatty amine containing tertiary amino, and the structural formula is as follows:
specifically, the anhydrous polar aprotic solvent is selected from one or more of N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) and dimethyl sulfoxide (DMSO).
Further, the structural formula of the tetrahalo monomer A is selected from the following substances:
the self-contained microporous polymer synthesized by the preparation method has the characteristics of strong adjustability of chemical structure, easily obtained raw materials, low price, simple synthesis steps and the like. The method not only can inherit and develop the advantage of high selectivity of the cyclic ammonium phenolphthalein polyarylethersulfone membrane in the process of recovering diffusion dialysis acid, but also is expected to have the advantages of excellent stability and high flux of microporous membrane materials, and has wide application prospect in the fields of gas separation, diffusion dialysis, electrodialysis and the like.
Detailed Description
The applicant researches and discovers that a series of Cardo type polymer self-possessed microporous diffusion dialysis membrane materials can be prepared on the basis of the structural characteristics of a cyclic ammonium type phenolphthalein polyarylethersulfone anion exchange membrane material.
The embodiment of the invention relates to a preparation method of a polymer with micropores, which comprises the following specific steps:
step 1: synthesis of tetraphenol monomer: in N 2 In the atmosphere, raw materials and raw material modifiers are mixed according to the mass ratio of 1: 2-7, the used solvents are polar aprotic solvents such as N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO) and the like, preferably DMAc, NMP and DMSO, the solvents are placed in a constant-temperature oil bath at the temperature of 100-200 ℃ to react for 1-10 d, the viscous solution is slowly poured into deionized water, and the deionized water is subjected to suction filtration and drying to obtain a crude product, and then recrystallization or column chromatography separation is carried out to obtain a corresponding tetraphenol monomer;
and 2, step: synthesis of the Polymer in N 2 In the atmosphere, reacting tetraphenol monomer, tetrahalo monomer A and NaOH or K 2 CO 3 Or Cs 2 CO 3 Or Na 2 CO 3 (preferably K) 2 CO 3 、Cs 2 CO 3 ) According to the mass ratio of 1:1: 2-9 (preferably 1MSO, preferably DMAc and NMP), toluene or cyclohexane are added into a reactor provided with a water separator together, the mixture is heated in a constant temperature oil bath at 120-130 ℃, the water generated by the reaction is brought out by the toluene or cyclohexane azeotropy, the azeotropic toluene (cyclohexane) is evaporated after the reaction is carried out for 2-3 h, the mixture is continuously heated in a constant temperature oil bath at 100-180 ℃, the viscous solution is slowly poured into deionized water after the reaction is carried out for 3-10 h, the suction filtration is carried out to obtain a fibrous polymer, the fibrous polymer is washed by distilled water for 3-5 times, and the fibrous polymer is dried to constant weight at 100-130 ℃ under the vacuum condition, so that the self-micropore polymer containing side chain amino is obtained.
The structural formula of the raw materials used in the step 1 is as follows:
the structural general formula of the raw material modifier selected in the step 1 is as follows:
NH 2 -R
wherein R has the structural formula:
in the formula, R 1 、R 2 And R 3 The group is an aliphatic chain structure consisting of 0-12C and O elements in length; wherein R is 2 The attachment position of the group on the cyclic amine ring is an arbitrary position.
The structural formula of the tetraphenol monomer prepared in step 1 is as follows:
wherein R is fatty amine containing tertiary amino, and the structural formula is as follows:
the structural formula of the tetrahalo monomer A in the step 2 is selected from the following substances:
the structure of the polymer with micropores prepared in the step 2 is shown as the following formula:
in the following examples, raw material modifications and raw materials were reacted to prepare tetraphenol monomers containing cardo group and cyclic amine group (the preparation of the cyclic amine tetraphenol monomers in the examples is described in Chinese patent application No. 201610883398). The preparation of the polymer matrix material containing cardo group and cyclic amine group is prepared by nucleophilic substitution reaction of the cyclic amine monomer and tetrahalogen monomer mentioned in the application, and the specific preparation method refers to Chinese patent application, application number: CN201911212624.9, application No.: 201911241996.4, application No.: 202010405412.9 (the preparation of the polymeric matrix material described in this application is described in the above published patent application).
The following are specific examples given by the inventors, and the preparation method of the polymer matrix material described in the subsequent examples of example 1 is the same as that of example 1.
Example 1:
step 1: at N 2 In the atmosphere, 15.95g of raw material 1 and 30g of 1- (2-aminoethyl) pyrrolidine are added into a 100mL three-necked flask, the flask is placed in a constant-temperature oil bath at 160 ℃ for reaction for 5d, the viscous solution is slowly poured into deionized water, and the deionized water is subjected to suction filtration and drying to obtain a crude product, and then the crude product is subjected to column chromatography separation to obtain a pure product of the raw material 1 tetraphenol monomer.
The structural formula is as follows:
step 2: in N 2 In a 100mL three-necked flask equipped with a water separator under an atmosphere protection, the raw materials 1 tetraphenol monomer (2.3024g, 5mmol), tetrafluoroterephthalonitrile (1.0005g, 5mmol), and K were charged into a flask 2 CO 3 (2.073 g, 15mmol) is dissolved in 10mL of anhydrous DMAc and 30mL of toluene mixed solvent, the mixture is heated in a constant temperature oil bath at 130 ℃, the toluene azeotropes to take out the water generated in the reaction, the mechanical stirring is carried out, after 2h, the azeotropic toluene is evaporated, the mixture is continuously heated in a constant temperature oil bath at 160 ℃, after 6h of reaction, the viscous solution is slowly poured into deionized water and is filtered by suction, the fibrous polymer is obtained, the fibrous polymer is washed by distilled water for 3 times, and the fibrous polymer is dried to constant weight at 100 ℃ under the vacuum condition, so that the self-microporous polymer is obtained.
The obtained self-microporous polymer has the following structural formula:
the yield of the polymer having micropores was 97.2%.
Example 2:
step 1: in N 2 In the atmosphere, 13.77g of raw material 1, 20g of N, N-dimethyl ethylenediamine are added into a 100mL three-necked flask, the flask is placed in a constant-temperature oil bath at 165 ℃ for reaction for 5 days, the viscous solution is slowly poured into deionized water, suction filtration and drying are carried out to obtain a crude product, and the crude product is separated by column chromatography to obtain the pure product of the raw material 1 tetraphenol monomer.
The structural formula is as follows:
step 2: in N 2 In a 100mL three-necked flask equipped with a water separator under an atmosphere protection, raw materials 1 tetraphenol monomer (2.1722g, 5 mmol), tetrafluoroterephthalonitrile (1.0005g, 5 mmol) and K were placed 2 CO 3 (2.073g, 15mmol) was dissolved in a mixed solvent of 10mL of anhydrous DMAc and 30mL of toluene, and the mixture was heated in an oil bath at a constant temperature of 130 ℃ with an azeotropic zone of tolueneAnd (3) taking out water generated in the reaction, mechanically stirring, evaporating azeotropic toluene after 2 hours, continuously heating in a constant-temperature oil bath at 160 ℃, after 5 hours of reaction, slowly pouring the viscous solution into deionized water, carrying out suction filtration to obtain a fibrous polymer, washing the fibrous polymer for 3 times by using distilled water, and drying at 100 ℃ under a vacuum condition to constant weight to obtain the self-micropore polymer.
The structural formula of the obtained polymer with micropores is shown as follows:
the yield of the polymer with micropores was 96.2%.
Example 3:
step 1: in N 2 In the atmosphere, 14.20g of raw material 1 and 30g of N- (2-aminoethyl) piperidine are added into a 100mL three-necked flask, the three-necked flask is placed in a constant-temperature oil bath at 160 ℃ for reaction for 7d, the viscous solution is slowly poured into deionized water, suction filtration and drying are carried out to obtain a crude product, and the crude product is separated by column chromatography to obtain the pure product of the raw material 1 tetraphenol monomer.
The structural formula is as follows:
step 2: at N 2 In a 100mL three-necked flask equipped with a water separator under an atmosphere protection, raw materials 1 tetraphenol monomer (2.3725g, 5 mmol), tetrafluoroterephthalonitrile (1.0005g, 5 mmol), and K were placed 2 CO 3 (2.073 g, 15mmol) is dissolved in 10mL of anhydrous DMAc and 30mL of toluene mixed solvent, the mixture is heated in a constant temperature oil bath at 130 ℃, the toluene azeotropes to take out the water generated in the reaction, the mechanical stirring is carried out, after 2h, the azeotropic toluene is evaporated, the mixture is continuously heated in a constant temperature oil bath at 170 ℃, after 5h of reaction, the viscous solution is slowly poured into deionized water and is filtered by suction, the fibrous polymer is obtained, the fibrous polymer is washed by distilled water for 3 times, and the fibrous polymer is dried to constant weight at 100 ℃ under the vacuum condition, so that the self-microporous polymer is obtained.
The obtained self-microporous polymer has the following structural formula:
the yield of the polymer having micropores was 97.6%.
Example 4:
step 1: at N 2 In the atmosphere, 13.99g of raw material 1 and 30g of N- (2-aminoethyl) morpholine are added into a 100mL three-necked flask, the three-necked flask is placed in a constant-temperature oil bath at 160 ℃ for reaction for 5 days, the viscous solution is slowly poured into deionized water, suction filtration and drying are carried out to obtain a crude product, and the crude product is separated by column chromatography to obtain a pure product of the raw material 1 tetraphenol monomer.
The structural formula is as follows:
and 2, step: in N 2 In a 100mL three-neck flask equipped with a water separator, raw materials 1 tetraphenol monomer (2.3824g, 5 mmol), tetrafluoroterephthalonitrile (1.0005g, 5 mmol), and K were placed under an atmosphere 2 CO 3 (2.073 g, 15mmol) is dissolved in 10mL of anhydrous DMAc and 30mL of toluene mixed solvent, the mixture is heated in a constant temperature oil bath at 130 ℃, the toluene azeotropes to take out the water generated in the reaction, the mechanical stirring is carried out, after 2h, the azeotropic toluene is evaporated, the mixture is continuously heated in a constant temperature oil bath at 165 ℃, after the reaction is carried out for 6h, the viscous solution is slowly poured into deionized water and is filtered by suction, the fibrous polymer is obtained, the fibrous polymer is washed by distilled water for 3 times, and the fibrous polymer is dried to constant weight at 100 ℃ under the vacuum condition, so that the self-microporous polymer is obtained.
The obtained self-microporous polymer has the following structural formula:
the yield of the polymer having micropores was 97.5%.
Example 5:
step 1: at N 2 In the atmosphere, 15.34g of raw material 2 and 30g of 1- (2-aminoethyl) pyrrolidine are added into a 100mL three-necked flask, the flask is placed in a constant-temperature oil bath at 160 ℃ for reaction for 5 days, the viscous solution is slowly poured into deionized water, suction filtration and drying are carried out to obtain a crude product, and the crude product is separated by column chromatography to obtain the pure product of the raw material 2 tetraphenol monomer.
The structural formula is as follows:
step 2: at N 2 In a 100mL three-neck flask with a water separator under the protection of atmosphere, raw materials 2, namely a tetraphenol monomer (2.2325g, 5mmol), tetrafluoroterephthalonitrile (1.0005g, 5mmol) and K are added 2 CO 3 (2.073 g, 15mmol) is dissolved in 10mL of anhydrous DMAc and 30mL of toluene mixed solvent, the mixture is heated in a constant temperature oil bath at 130 ℃, the toluene azeotropes to take out the water generated in the reaction, the mechanical stirring is carried out, after 2h, the azeotropic toluene is evaporated, the mixture is continuously heated in a constant temperature oil bath at 160 ℃, after 8h of reaction, the viscous solution is slowly poured into deionized water and is filtered by suction, the fibrous polymer is obtained, the fibrous polymer is washed by distilled water for 3 times, and the fibrous polymer is dried to constant weight at 100 ℃ under the vacuum condition, so that the self-microporous polymer is obtained.
The obtained self-microporous polymer has the following structural formula:
the yield of the polymer having micropores was 95.3%.
Example 6:
step 1: in N 2 In the atmosphere, 13.45g of raw material 2 and 30g of N- (2-aminoethyl) morpholine are added into a 100mL three-necked flask, the flask is placed in a constant-temperature oil bath at 160 ℃ for reaction for 6d, the viscous solution is slowly poured into deionized water, suction filtration and drying are carried out to obtain a crude product, and the crude product is separated by column chromatography to obtain a pure product of the raw material 2 tetraphenol monomer.
The structural formula is as follows:
step 2: in N 2 In a 100mL three-necked flask equipped with a water separator under an atmosphere protection, raw materials 2 tetraphenol monomer (2.3125g, 5 mmol), tetrafluoroterephthalonitrile (1.0005g, 5 mmol), and K were placed 2 CO 3 (2.073g, 15mmol) is dissolved in 10mL of anhydrous DMAc and 30mL of toluene mixed solvent, the mixture is heated in a constant temperature oil bath at 130 ℃, the toluene takes out the water generated in the reaction by azeotropy, the mechanical stirring is carried out, after 2h, the azeotropic toluene is evaporated, the mixture is continuously heated in a constant temperature oil bath at 165 ℃, after 8h of reaction, the viscous solution is slowly poured into deionized water, the filtration is carried out, the fibrous polymer is obtained, the distilled water is used for washing the fibrous polymer for 3 times, and the fibrous polymer is dried to constant weight at 100 ℃ under the vacuum condition, so that the microporous polymer is obtained.
The obtained self-microporous polymer has the following structural formula:
the yield of the polymer having micropores was 98.5%.
Example 7:
step 1: in N 2 In the atmosphere, 14.53g of raw material 3 and 30g of N- (2-aminoethyl) morpholine are added into a 100mL three-necked flask, the three-necked flask is placed in a constant-temperature oil bath at 160 ℃ for reaction for 5 days, the viscous solution is slowly poured into deionized water, suction filtration and drying are carried out to obtain a crude product, and the crude product is separated by column chromatography to obtain a pure product of the raw material 3 tetraphenol monomer.
The structural formula is as follows:
and 2, step: in N 2 In a 100mL three-neck flask with a water separator, under the protection of atmosphere, raw material 3-tetraphenol monomer (2.4527g, 5 mmol),Tetrafluoroterephthalonitrile (1.0005g, 5mmol), K 2 CO 3 (2.073g, 15mmol) is dissolved in 10mL of anhydrous DMAc and 30mL of toluene mixed solvent, the mixture is heated in a constant temperature oil bath at 130 ℃, the toluene takes out the water generated in the reaction by azeotropy, the mechanical stirring is carried out, after 2h, the azeotropic toluene is evaporated, the mixture is continuously heated in a constant temperature oil bath at 165 ℃, after 7h of reaction, the viscous solution is slowly poured into deionized water, the filtration is carried out, the fibrous polymer is obtained, the distilled water is used for washing the fibrous polymer for 3 times, and the fibrous polymer is dried to constant weight at 100 ℃ under the vacuum condition, so that the microporous polymer is obtained.
The obtained self-microporous polymer has the following structural formula:
the yield of the polymer with micropores was 96.5%.
Example 8:
step 1: in N 2 Adding 16.56g of raw material 3 and 30g of 1- (2-aminoethyl) pyrrolidine into a 100mL three-necked flask in an atmosphere, placing the flask in a constant-temperature oil bath at 160 ℃ for reaction for 5d, slowly pouring the viscous solution into deionized water, performing suction filtration and drying to obtain a crude product, and performing column chromatography separation to obtain a pure product of the raw material 3 tetraphenol monomer.
The structural formula is as follows:
step 2: in N 2 In a 100mL three-necked flask equipped with a water separator under an atmosphere protection, the raw materials 3 tetraphenol monomer (2.3727g, 5 mmol), tetrafluoroterephthalonitrile (1.0005g, 5 mmol), and K were placed 2 CO 3 (2.073g, 15mmol) is dissolved in 10mL of anhydrous DMAc and 30mL of toluene mixed solvent, the mixture is heated in a constant temperature oil bath at 130 ℃, the toluene takes out the water generated in the reaction by azeotropy, the mechanical stirring is carried out, after 2h, the azeotropic toluene is evaporated, the mixture is continuously heated in a constant temperature oil bath at 160 ℃, after the reaction is carried out for 6h, the viscous solution is slowly poured into deionized water, and the filtration is carried out to obtain fibrous solutionWashing the polymer with distilled water for 3 times, and drying at 100 deg.C under vacuum condition to constant weight to obtain the final product.
The obtained self-microporous polymer has the following structural formula:
the yield of the polymer having micropores was 96.8%.
Example 9:
step 1: in N 2 In the atmosphere, 15.95g of raw material 1 and 30g of 1- (2-aminoethyl) pyrrolidine are added into a 100mL three-necked flask, the flask is placed in a constant-temperature oil bath at 160 ℃ for reaction for 5d, the viscous solution is slowly poured into deionized water, and the deionized water is subjected to suction filtration and drying to obtain a crude product, and then the crude product is subjected to column chromatography separation to obtain a pure product of the raw material 1 tetraphenol monomer.
The structural formula is as follows:
step 2: in N 2 In a 100mL three-necked flask equipped with a water separator under an atmosphere protection, the starting materials 1 tetraphenol monomer (2.3024g, 5mmol), 2,3,5, 6-tetrafluoropyridine-4-carbonitrile (0.8803g, 5mmol), and K were charged 2 CO 3 (2.073 g, 15mmol) is dissolved in 10mL of anhydrous DMAc and 30mL of toluene mixed solvent, the mixture is heated in a constant temperature oil bath at 130 ℃, the toluene azeotropes to take out the water generated in the reaction, the mechanical stirring is carried out, after 2h, the azeotropic toluene is evaporated, the mixture is continuously heated in a constant temperature oil bath at 160 ℃, after 8h of reaction, the viscous solution is slowly poured into deionized water and is filtered by suction, a fibrous polymer is obtained, the polymer is washed by distilled water for 3 times, and the polymer is dried to constant weight at 100 ℃ under the vacuum condition, thus obtaining the self-microporous polymer.
The obtained self-microporous polymer has the following structural formula:
the yield of the polymer having micropores was 98.6%.
Example 10:
step 1: in N 2 In the atmosphere, 15.34g of raw material 2 and 30g of 1- (2-aminoethyl) pyrrolidine are added into a 100mL three-necked flask, the flask is placed in a constant-temperature oil bath at 160 ℃ for reaction for 5 days, the viscous solution is slowly poured into deionized water, and the deionized water is subjected to suction filtration and drying to obtain a crude product, and then the crude product is subjected to column chromatography separation to obtain a pure product of the raw material 2 tetraphenol monomer.
The structural formula is as follows:
step 2: in N 2 In a 100mL three-necked flask equipped with a water separator under protection of atmosphere, starting materials 2 tetraphenol monomer (2.2325g, 5 mmol), 2,3,5, 6-tetrafluoropyridine-4-carbonitrile (0.8803g, 5 mmol), and K 2 CO 3 (2.073g, 15mmol) is dissolved in 10mL of anhydrous DMAc and 30mL of toluene mixed solvent, the mixture is heated in a constant temperature oil bath at 130 ℃, the toluene takes out the water generated in the reaction by azeotropy, the mechanical stirring is carried out, after 2h, the azeotropic toluene is evaporated, the mixture is continuously heated in a constant temperature oil bath at 160 ℃, after 8h of reaction, the viscous solution is slowly poured into deionized water, the filtration is carried out, a fibrous polymer is obtained, the polymer is washed by distilled water for 3 times, and the polymer is dried to constant weight at 100 ℃ under the vacuum condition, so that the microporous polymer is obtained.
The obtained self-microporous polymer has the following structural formula:
the yield of the polymer having micropores was 97.2%.
Example 11:
step 1: in N 2 In an atmosphere, 14.20g of raw material 1 and 30g of N- (2-aminoethyl) piperidine were put in a 100mL three-necked flask, and after reaction in a 160 ℃ constant temperature oil bath for 7 days, the viscous liquid was put inSlowly pouring the solution into deionized water, carrying out suction filtration, drying to obtain a crude product, and carrying out column chromatography separation to obtain a pure product of the raw material 1 tetraphenol monomer.
The structural formula is as follows:
and 2, step: in N 2 In a 100mL three-necked flask equipped with a water separator under protection of atmosphere, starting materials 1 tetraphenol monomer (2.3725g, 5 mmol), 2,3,5, 6-tetrafluoropyridine-4-carbonitrile (0.8803g, 5 mmol), and K 2 CO 3 (2.073g, 15mmol) is dissolved in 10mL of anhydrous DMAc and 30mL of toluene mixed solvent, the mixture is heated in a constant temperature oil bath at 130 ℃, the toluene takes out the water generated in the reaction by azeotropy, the mechanical stirring is carried out, after 2h, the azeotropic toluene is evaporated, the mixture is continuously heated in a constant temperature oil bath at 170 ℃, after 7h of reaction, the viscous solution is slowly poured into deionized water, the filtration is carried out, a fibrous polymer is obtained, the polymer is washed by distilled water for 3 times, and the polymer is dried to constant weight at 100 ℃ under the vacuum condition, so that the microporous polymer is obtained.
The resulting self-polymerized microporous polymer has the following structural formula:
the yield of the polymer having micropores was 95.9%.
The above embodiments are preferred examples of the present invention, and the present invention is not limited to these embodiments, and any addition and equivalent changes made on the basis of the technical solutions of the present application should fall within the protection scope defined by the claims of the present invention.
Claims (4)
1. The preparation method of the polymer with micropores is characterized in that the method comprises the steps of mixing a tetraphenol monomer, a tetrahalogen monomer A and NaOH or K 2 CO 3 Or Cs 2 CO 3 Or Na 2 CO 3 According to the mass ratio of 1:1:2 to 9, and then mixing with a proper amount of anhydrous polar non-polar solventAdding a proton solvent and toluene or cyclohexane into a reactor provided with a water separator together, heating in a constant-temperature oil bath at 120-130 ℃, azeotropically taking out water generated by the reaction, reacting for 2-3 h, evaporating out the azeotropic toluene or cyclohexane, continuing heating in a constant-temperature oil bath at 100-180 ℃, reacting for 3-10 h, slowly pouring the viscous solution into deionized water, performing suction filtration to obtain a fibrous polymer, washing the fibrous polymer with distilled water for 3-5 times, and drying at 100-130 ℃ under a vacuum condition to constant weight to obtain a self-micropore polymer containing side chain amino; wherein:
the synthetic method of the tetraphenol monomer is that N is 2 In the atmosphere, raw materials and raw material modifiers are mixed according to the mass ratio of 1: 2-7, reacting in a constant temperature oil bath at 100-200 ℃ for 1-10 d by using a polar aprotic solvent, slowly pouring the reacted viscous solution into deionized water, performing suction filtration, drying to obtain a crude product, and performing recrystallization or column chromatographic separation to obtain a corresponding tetraphenol monomer;
the structural formula of the raw material is as follows:
the structural general formula of the raw material modifier is as follows:
NH 2 -R；
wherein R has the structural formula:
in the formula, R 1 、R 2 And R 3 The group is an aliphatic chain structure consisting of 0-12C and O elements in length, wherein R 2 The connecting position of the group on the cyclic amine ring is any position;
the structure of the prepared polymer with micropores is shown as the following formula:
2. the method of claim 1, wherein the tetraphenol monomer prepared has the formula:
in the formula, R is fatty amine containing tertiary amino, and the structural formula is as follows:
3. the method according to claim 1, wherein the anhydrous polar aprotic solvent is selected from one or more of N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), and Dimethylsulfoxide (DMSO).
4. The method of claim 1, wherein the tetrahalo monomer a has a formula selected from the group consisting of:
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